JP2024520576A - Polylactide resin composition having excellent crystallization half-life and method for producing same - Google Patents
Polylactide resin composition having excellent crystallization half-life and method for producing same Download PDFInfo
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 77
- 238000002425 crystallisation Methods 0.000 title claims abstract description 46
- 230000008025 crystallization Effects 0.000 title claims abstract description 46
- 239000011342 resin composition Substances 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title description 7
- 239000002667 nucleating agent Substances 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 32
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 9
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical group O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 229940035893 uracil Drugs 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 239000004626 polylactic acid Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 description 1
- KGLPWQKSKUVKMJ-UHFFFAOYSA-N 2,3-dihydrophthalazine-1,4-dione Chemical compound C1=CC=C2C(=O)NNC(=O)C2=C1 KGLPWQKSKUVKMJ-UHFFFAOYSA-N 0.000 description 1
- RBMHUYBJIYNRLY-UHFFFAOYSA-N 2-[(1-carboxy-1-hydroxyethyl)-hydroxyphosphoryl]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)(C)P(O)(=O)C(C)(O)C(O)=O RBMHUYBJIYNRLY-UHFFFAOYSA-N 0.000 description 1
- KSILMCDYDAKOJD-UHFFFAOYSA-N 2-aminoisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(N)C(=O)C2=C1 KSILMCDYDAKOJD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- -1 cadmium phenylmalonate Chemical compound 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940022769 d- lactic acid Drugs 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001434 poly(D-lactide) Polymers 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
本発明は、特定の核剤を組み合わせて使用するポリラクチド樹脂組成物に関し、結晶化半減期および結晶化度に優れるため、加工性に優れると共に、本発明によるポリラクチド樹脂固有の特性を維持することができる。The present invention relates to a polylactide resin composition using a specific nucleating agent in combination, which has excellent crystallization half-life and crystallinity, and therefore has excellent processability while maintaining the properties inherent to the polylactide resin according to the present invention.
Description
関連出願（ら）との相互引用
本出願は、２０２２年３月２２日付韓国特許出願第１０－２０２２－００３５５５３号に基づいた優先権の利益を主張し、当該韓国特許出願の文献に開示された全ての内容は本明細書の一部として含まれる。
Cross-Citation with Related Application(s) This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0035553 dated March 22, 2022, and all contents disclosed in the documents of said Korean patent application are incorporated herein by reference.
本発明は、結晶化半減期に優れたポリラクチド樹脂組成物およびその製造方法に関する。 The present invention relates to a polylactide resin composition having an excellent crystallization half-life and a method for producing the same.
ポリラクチド（または、ポリ乳酸；ＰＬＡ）樹脂は、バイオ原料をベースとして製造されるものであり、製造過程で地球温暖化ガスである二酸化炭素の排出が少なく、また特定の温度と堆肥化設備により分解される特徴を有するエコ素材である。また、最近は、廃プラスチックの使用および炭素排出規制に対する対応案として既存の原油ベースの樹脂を代替できる素材の中の一つとして注目されている。 Polylactide (or polylactic acid; PLA) resin is manufactured from bio-based raw materials, and is an eco-friendly material that emits little carbon dioxide, a greenhouse gas, during the manufacturing process and decomposes at specific temperatures in composting equipment. Recently, it has also been attracting attention as one of the materials that can replace existing crude oil-based resins as a response to the use of waste plastics and carbon emission regulations.
また、ポリラクチド樹脂は、他の生分解性高分子に比べて安価であり、高い引張強度とモジュラス特性を有しているという長所がある。 Polylactide resin also has the advantage of being cheaper than other biodegradable polymers and having high tensile strength and modulus properties.
しかし、ポリラクチド樹脂は、リジッドな（ｒｉｇｉｄ）高分子主鎖が短い単位で繰り返され、遅い連鎖（ｃｈａｉｎ）移動性により結晶化速度が遅いため成形サイクルが長く、そのために生産性が落ちるという問題点がある。したがって、このような問題点を改善するために、核剤のような物質を導入して生産性と耐熱性を改善させるための研究が多く行われている。 However, polylactide resin has a problem in that the rigid polymer backbone is repeated in short units and the crystallization speed is slow due to slow chain mobility, resulting in a long molding cycle and low productivity. Therefore, in order to solve these problems, much research is being conducted to improve productivity and heat resistance by introducing substances such as nucleating agents.
一般的に、前記核剤として使用される物質は、主に無機系核剤であり、タルク（Ｔａｌｃ）、マイカ（Ｍｉｃａ）、ナノクレイ（ｎａｎｏｃｌａｙ）のような物質が使用され、これをＰＬＡの成形時に一部を添加して耐熱性と強度を改善することができることが報告されている。しかし、このような核剤を過量で添加すると樹脂比重の増加と透明性が落ちるという問題がある。一方、結晶性と透明性を向上させる物質としてＬＡＫ３０１（ａｒｏｍａｔｉｃ ｓｕｌｆｏｎａｔｅ ｄｒｉｖａｔｅ）、安息香酸ナトリウム（ｓｏｄｉｕｍ ｂｅｎｚｏａｔｅ）、 Ｎ－アミノフタルイミド（Ｎ－ａｍｉｎｏｐｈｔｈａｌｉｍｉｄｅ）、フタルヒドラジド（ｐｈｔｈａｌｈｙｄｒａｚｉｄｅ）、フェニルマロン酸カドミウム（ｃａｄｍｉｕｍ ｐｈｅｎｙｌｍａｌｏｎａｔｅ）などのような有機系核剤が使用されている。しかし、このような物質は、バイオベースの物質でなく、ＰＬＡ樹脂と分散の問題が存在する。 Generally, the materials used as the nucleating agent are mainly inorganic nucleating agents such as talc, mica, and nanoclay, and it has been reported that adding some of these nucleating agents during molding of PLA can improve heat resistance and strength. However, adding an excessive amount of such nucleating agents increases the resin specific gravity and reduces transparency. Meanwhile, organic nucleating agents such as LAK301 (aromatic sulfonate drivate), sodium benzoate, N-aminophthalimide, phthalhydrazide, and cadmium phenylmalonate are used as materials for improving crystallinity and transparency. However, such materials are not bio-based and have dispersion issues with PLA resins.
したがって、エコ製品として製造することができ、同時に透明性を阻害しないバイオベースの有機系核剤を導入する必要がある。また、ポリラクチド樹脂と分散の問題が少ない核剤を導入してポリラクチド樹脂の結晶化半減期および結晶化度を追加的に改善することが必要である。 Therefore, it is necessary to introduce a bio-based organic nucleating agent that can be manufactured as an eco-product and at the same time does not impair transparency. It is also necessary to introduce a nucleating agent that has fewer dispersion problems with polylactide resin to additionally improve the crystallization half-life and crystallinity of polylactide resin.
本発明は、特定の核剤を組み合わせて使用して結晶化半減期に優れたポリラクチド樹脂組成物を提供するものである。 The present invention provides a polylactide resin composition with excellent crystallization half-life by using a combination of specific nucleating agents.
また、本発明は、前記ポリラクチド樹脂組成物の製造方法に関するものである。 The present invention also relates to a method for producing the polylactide resin composition.
前記課題を解決するために、本発明は、下記のポリラクチド樹脂組成物を提供する。 In order to solve the above problems, the present invention provides the following polylactide resin composition.
ポリラクチド樹脂；第１核剤；および第２核剤を含む、ポリラクチド樹脂組成物において、
前記ポリラクチド樹脂組成物は、１００～１３０℃の結晶化温度で結晶化半減期が２分以下である、
ポリラクチド樹脂組成物。
A polylactide resin composition comprising: a polylactide resin; a first nucleating agent; and a second nucleating agent,
The polylactide resin composition has a crystallization half-life of 2 minutes or less at a crystallization temperature of 100 to 130°C.
Polylactide resin composition.
本発明で使用する用語「ポリラクチド樹脂」とは、下記の繰り返し単位を含む単一重合体または共重合体を包括して称するものと定義される。
前記ポリラクチド樹脂は、ラクチド単量体の開環重合により前記繰り返し単位を形成する段階を含んで製造され得、このような開環重合および前記繰り返し単位の形成工程が完了した後の重合体を前記「ポリラクチド樹脂」と称することができる。 The polylactide resin can be produced by a process that includes forming the repeating units by ring-opening polymerization of lactide monomers, and the polymer obtained after the ring-opening polymerization and the process of forming the repeating units are completed can be called the "polylactide resin."
この時、「ラクチド単量体」は、次のとおり定義され得る。通常、ラクチドは、Ｌ－乳酸からなるＬ－ラクチド、Ｄ－乳酸からなるＤ－ラクチド、Ｌ－形態とＤ－形態がそれぞれ一つずつからなるｍｅｓｏラクチドに区分され得る。また、Ｌ－ラクチドとＤ－ラクチドが５０：５０で混合されているものをＤ、Ｌ－ラクチドまたはｒａｃ－ラクチドという。これらラクチドのうち、光学的純度が高いＬ－ラクチドまたはＤ－ラクチドのみを利用して重合を行う場合、立体規則性が非常に高いＬ－またはＤ－ポリラクチド（ＰＬＬＡまたはＰＤＬＡ）が得られると知られており、このようなポリラクチドは、光学的純度が低いポリラクチドに比べて結晶化速度が速く、結晶化度も高いと知られている。ただし、本明細書で「ラクチド単量体」とは、各形態によるラクチドの特性の違いおよびこれから形成されたポリラクチド樹脂の特性の違いに関係なく全ての形態のラクチドを含むものと定義される。 In this case, the term "lactide monomer" can be defined as follows. Lactide can be generally classified into L-lactide consisting of L-lactic acid, D-lactide consisting of D-lactic acid, and meso-lactide consisting of one L-form and one D-form. A 50:50 mixture of L-lactide and D-lactide is called D,L-lactide or rac-lactide. It is known that when polymerization is carried out using only L-lactide or D-lactide having high optical purity among these lactides, L- or D-polylactide (PLLA or PDLA) with very high stereoregularity can be obtained, and such polylactide is known to have a faster crystallization rate and a higher degree of crystallization than polylactide having low optical purity. However, in this specification, "lactide monomer" is defined to include all forms of lactide, regardless of the differences in the properties of lactide according to each form and the differences in the properties of polylactide resins formed therefrom.
一方、本発明によるポリラクチド樹脂は、一例として重量平均分子量が７０，０００～４００，０００である。 On the other hand, the polylactide resin according to the present invention has, for example, a weight average molecular weight of 70,000 to 400,000.
本発明は、このようなポリラクチド樹脂に前記第１核剤と第２核剤を共に使用することによって、ポリラクチド樹脂の結晶化半減期を改善することを特徴とする。 The present invention is characterized in that the crystallization half-life of such a polylactide resin is improved by using both the first nucleating agent and the second nucleating agent in the polylactide resin.
特に、前記ポリラクチド樹脂組成物は、１００～１３０℃の結晶化温度で結晶化半減期が５分以下であることを特徴とする。好ましくは、前記結晶化半減期が１．９分以下、１．８分以下、１．７分以下、１．６分以下、１．５分以下、１．４分以下、１．３分以下、１．２分以下、１．１分以下、または、１．０分以下である。また、前記結晶化半減期は、０．１分以上、０．２分以上、０．３分以上、０．４分以上、または、０．５分以上である。 In particular, the polylactide resin composition is characterized in that it has a crystallization half-life of 5 minutes or less at a crystallization temperature of 100 to 130°C. Preferably, the crystallization half-life is 1.9 minutes or less, 1.8 minutes or less, 1.7 minutes or less, 1.6 minutes or less, 1.5 minutes or less, 1.4 minutes or less, 1.3 minutes or less, 1.2 minutes or less, 1.1 minutes or less, or 1.0 minutes or less. In addition, the crystallization half-life is 0.1 minutes or more, 0.2 minutes or more, 0.3 minutes or more, 0.4 minutes or more, or 0.5 minutes or more.
本発明で使用する用語「結晶化半減期（Ｃｒｙｓｔａｌｌｉｚａｔｉｏｎ ｈａｌｆ－ｔｉｍｅ（ｔ１／２））は、結晶化が５０％行われるまでかかる時間（分）を意味し、相対的な結晶化速度を評価するに有用な指標である。結晶化半減期を求めるためには、まず相対結晶化度（Ｒｅｌａｔｉｖｅ ｃｒｙｓｔａｌｌｉｎｉｔｙ）を求める。相対結晶化度は、等温結晶化過程での時間に応じた発熱ピークで全体面積（ａｒｅａ）に対する時間ｔが過ぎた時の面積（ａｒｅａ）の比率を意味し、時間に応じた相対結晶化度に変換後に相対結晶化度が０．５になる時の時間を結晶化半減期として求めることができる。このような過程を図１に図式的に示し、より詳細な測定方法は後述する実施例で具体化することができる。 The term "crystallization half-time (t 1/2 )" used in the present invention means the time (minutes) required for 50% crystallization to occur, and is a useful index for evaluating the relative crystallization rate. In order to determine the crystallization half-life, first, the relative crystallinity is determined. The relative crystallinity means the ratio of the area at the time t to the total area at the exothermic peak as a function of time during isothermal crystallization, and the time when the relative crystallinity becomes 0.5 after conversion to the relative crystallinity as a function of time can be determined as the crystallization half-life. This process is diagrammatically shown in FIG. 1, and a more detailed measurement method can be embodied in the examples described below.
本発明で使用する用語「結晶化温度」とは、前記結晶化半減期を測定するためにポリラクチド樹脂を所定の温度に溶融させた後に冷却する時の温度を意味する。例えば、ポリラクチド樹脂を２００℃に溶融させた後、４０℃／ｍｉｎ～１００℃／ｍｉｎの冷却速度で１２０℃まで冷却する時、前記１２０℃を「結晶化温度」という。本発明では前記結晶化温度は、１００～１３０℃であり、一例として１００℃、１１０℃、１２０℃、または、１３０℃である。前記結晶化温度による結晶化半減期の具体的な測定方法は以下の実施例に具体化することができる。 The term "crystallization temperature" used in the present invention means the temperature at which polylactide resin is cooled after melting it to a predetermined temperature in order to measure the crystallization half-life. For example, when polylactide resin is melted at 200°C and then cooled to 120°C at a cooling rate of 40°C/min to 100°C/min, the 120°C is called the "crystallization temperature". In the present invention, the crystallization temperature is 100 to 130°C, and examples include 100°C, 110°C, 120°C, or 130°C. A specific method for measuring the crystallization half-life according to the crystallization temperature can be embodied in the following examples.
好ましくは、本発明による前記ポリラクチド樹脂組成物は、１００～１３０℃の結晶化温度で結晶化度が３５％以上である。先に説明したとおり、本発明による前記ポリラクチド樹脂組成物は、結晶化半減期はもちろん、結晶化度も優れるという特徴がある。好ましくは、前記結晶化度が４０％以上、４５％以上、または、５０％以上である。前記結晶化度の測定方法は以下の実施例に具体化することができる。 Preferably, the polylactide resin composition according to the present invention has a degree of crystallinity of 35% or more at a crystallization temperature of 100 to 130°C. As explained above, the polylactide resin composition according to the present invention is characterized by an excellent degree of crystallinity as well as a crystallization half-life. Preferably, the degree of crystallinity is 40% or more, 45% or more, or 50% or more. The method for measuring the degree of crystallinity can be embodied in the following examples.
一方、前記第１核剤は、ウラシル（ｕｒａｃｉｌ）である。前記第１核剤は、バイオベースの有機系物質であって、ポリラクチド樹脂に添加されて核生成部位（ｎｕｃｌｅａｔｉｏｎ ｓｉｔｅ）として作用して高い温度で結晶核生成を誘発して結晶化半減期および結晶化度を改善することができる。 Meanwhile, the first nucleating agent is uracil. The first nucleating agent is a bio-based organic material that is added to the polylactide resin and acts as a nucleation site to induce crystal nucleation at high temperatures, thereby improving the crystallization half-life and degree of crystallization.
好ましくは、前記第１核剤は、前記ポリラクチド樹脂組成物総重量に対して０．１～５重量％で含まれる。前記含有量が０．１重量％未満である場合には前記第１核剤の使用効果が微々であり、前記含有量が５重量％を超える場合にはポリラクチド樹脂固有の物性を阻害する恐れがある。より好ましくは、前記第１核剤は、前記ポリラクチド樹脂組成物総重量に対して０．２重量％以上、０．３重量％以上、０．４重量％以上、または、０．５重量％以上であり；４．５重量％以下、４．０重量％以下、または、３．５重量％以下含まれる。 Preferably, the first nucleating agent is contained in an amount of 0.1 to 5 wt % based on the total weight of the polylactide resin composition. If the content is less than 0.1 wt %, the effect of using the first nucleating agent is negligible, and if the content is more than 5 wt %, there is a risk of impairing the inherent physical properties of the polylactide resin. More preferably, the first nucleating agent is contained in an amount of 0.2 wt % or more, 0.3 wt % or more, 0.4 wt % or more, or 0.5 wt % or more based on the total weight of the polylactide resin composition; or 4.5 wt % or less, 4.0 wt % or less, or 3.5 wt % or less.
前記第２核剤は、ラクチド単量体のオリゴマー構造を含む核剤であって、このようなラクチド単量体のオリゴマー構造によりポリラクチド樹脂と相溶性が高いため、ポリラクチド樹脂に添加されて可塑剤と類似する役割を果たすようになる。そのためにポリラクチド樹脂内で自由体積（ｆｒｅｅ ｖｏｌｕｍｅ）を形成してポリラクチド樹脂の連鎖（ｃｈａｉｎ）移動性を向上させて結晶化半減期および結晶化度を改善することができる。 The second nucleating agent is a nucleating agent containing an oligomer structure of lactide monomer. Due to this oligomer structure of lactide monomer, it has high compatibility with polylactide resin and is added to polylactide resin to play a role similar to that of a plasticizer. Therefore, it can form free volume in the polylactide resin to improve the chain mobility of the polylactide resin and improve the crystallization half-life and degree of crystallization.
好ましくは、前記第２核剤は、下記の化学式１で表される化合物である。
［化学式１］
Ｌは、下記であり、
ｎ１は、１～３０の整数であり、
Ｒは、下記の化学式２で表される置換基であり、
［化学式２］
Ｒ’は、水素、またはアセチルである。
Preferably, the second nucleating agent is a compound represented by the following Formula 1:
[Chemical Formula 1]
L is as follows:
n1 is an integer from 1 to 30,
R is a substituent represented by the following chemical formula 2:
[Chemical Formula 2]
R' is hydrogen or acetyl.
前記第２核剤の重量平均分子量は、各ラクチド繰り返し単位数により調節され得る。好ましくは、前記第２核剤の重量平均分子量は、１，０００～５０，０００である。より好ましくは、前記第２核剤の重量平均分子量は、１，１００以上、１，２００以上、１，３００以上、１，４００以上、または、１，５００以上であり；４０，０００以下、３０，０００以下、２０，０００以下、１０，０００以下、９，０００以下、または、８，０００以下である。 The weight average molecular weight of the second nucleating agent can be adjusted by the number of each lactide repeat unit. Preferably, the weight average molecular weight of the second nucleating agent is 1,000 to 50,000. More preferably, the weight average molecular weight of the second nucleating agent is 1,100 or more, 1,200 or more, 1,300 or more, 1,400 or more, or 1,500 or more; 40,000 or less, 30,000 or less, 20,000 or less, 10,000 or less, 9,000 or less, or 8,000 or less.
好ましくは、前記第２核剤は、前記ポリラクチド樹脂組成物総重量に対して３～２５重量％で含まれる。前記含有量が３重量％未満である場合には前記第２核剤の使用効果が微々たるものであり、前記含有量が２５重量％を超える場合にはポリラクチド樹脂固有の物性を阻害する恐れがある。より好ましくは、前記第２核剤は、前記ポリラクチド樹脂組成物総重量に対して３．５重量％以上、４．０重量％以上、または、４．５重量％以上であり；２４重量％以下、２３重量％以下、２２重量％以下、または、２１重量％以下含まれる。 Preferably, the second nucleating agent is contained in an amount of 3 to 25% by weight based on the total weight of the polylactide resin composition. If the content is less than 3% by weight, the effect of using the second nucleating agent is negligible, and if the content is more than 25% by weight, there is a risk of impairing the inherent physical properties of the polylactide resin. More preferably, the second nucleating agent is contained in an amount of 3.5% by weight or more, 4.0% by weight or more, or 4.5% by weight or more based on the total weight of the polylactide resin composition; or 24% by weight or less, 23% by weight or less, 22% by weight or less, or 21% by weight or less.
一方、上述の本発明によるポリラクチド樹脂組成物の製造方法は、上述のポリラクチド樹脂、第１核剤、および第２核剤を混合する方法であれば特に制限されない。一例として、前記各成分は、溶融混合（ｍｅｌｔ ｂｌｅｎｄｉｎｇ）方法で製造することができる。 Meanwhile, the method for producing the polylactide resin composition according to the present invention is not particularly limited as long as it is a method for mixing the polylactide resin, the first nucleating agent, and the second nucleating agent. As an example, each of the components can be produced by a melt blending method.
上述の本発明によるポリラクチド樹脂組成物は、結晶化半減期および結晶化度に優れている。したがって、本発明によるポリラクチド樹脂組成物は、加工性に優れると共に、本発明によるポリラクチド樹脂固有の特性を維持することができる。 The polylactide resin composition according to the present invention described above has excellent crystallization half-life and crystallinity. Therefore, the polylactide resin composition according to the present invention has excellent processability and can maintain the inherent properties of the polylactide resin according to the present invention.
以下、本発明の実施形態を下記の実施例でより詳細に説明する。ただし、下記の実施例は、本発明の実施形態を例示するものに過ぎず、本発明の内容が下記の実施例により限定されるのではない。 Hereinafter, the embodiments of the present invention will be described in more detail with reference to the following examples. However, the following examples are merely illustrative of the embodiments of the present invention, and the contents of the present invention are not limited to the following examples.
製造例：第２核剤（Ｐ１０－Ａ－００２の製造）
ＰＥＧ－１０００（Ｐ１０）を開始剤として使用してオリゴマー（ｏｌｉｇｏｍｅｒ）を製造した。具体的には、２０ｍＬバイアル（ｖｉａｌ）にラクチド（Ｌａｃｔｉｄｅ）：Ｐ１０のモル比が８：１（モル比）で合計４．５ｇになるようにそれぞれ入れ、Ｓｎ（Ｏｃｔ）２触媒を０．１～０．２ｗｔ％になるように投入した後、１３０℃で４時間反応させた。温度を１２０℃に調節した後、無水酢酸（ａｃｅｔｉｃ ａｎｈｙｄｒｉｄｅ）（末端基ＯＨ基に対して４当量）を投入し、１２時間反応を追加的に行った。反応終了後、真空乾燥で副産物である酢酸（ａｃｅｔｉｃ ａｃｉｄ）および残留の無水酢酸（ａｃｅｔｉｃ ａｎｈｙｄｒｉｄｅ）を除去して末端基がアセチル（ａｃｅｔｙｌ）基で置換された構造を有する第２核剤を製造し、これをＰ１０－Ａ－００２と命名し、重量平均分子量は以下表１に示した。
Production Example: Second nucleating agent (production of P10-A-002)
An oligomer was prepared using PEG-1000 (P10) as an initiator. Specifically, lactide:P10 was placed in a 20 mL vial in a total amount of 4.5 g with a molar ratio of 8:1, and Sn(Oct) 2 catalyst was added to the mixture in an amount of 0.1-0.2 wt%, and the mixture was reacted at 130°C for 4 hours. The temperature was then adjusted to 120°C, and acetic anhydride (4 equivalents relative to the terminal OH group) was added, and the reaction was continued for an additional 12 hours. After the reaction was completed, the by-product acetic acid and residual acetic anhydride were removed by vacuum drying to prepare a second nucleating agent having a structure in which the terminal group was substituted with an acetyl group. This was named P10-A-002, and its weight average molecular weight is shown in Table 1 below.
実施例および比較例
Ｈａａｋｅミキサ（Ｍｉｘｅｒ）装備を活用して溶融混合（ｍｅｌｔ ｂｌｅｎｄｉｎｇ）を行った。具体的には、ＰＬＡペレット（ｐｅｌｌｅｔ）（ＮａｔｕｒｅＷｏｒｋｓ社の４０３２Ｄ；重量平均分子量約２００，０００）６５ｇを入れ、下記表１に記載された第１核剤および第２核剤を各含有量により投入した。パウダー（Ｐｏｗｄｅｒ）形態の核剤はＰＬＡペレット（ｐｅｌｌｅｔ）と混合して投入し、工程運転温度（１８０℃）よりも低い融点を有する核剤は混合（ｂｌｅｎｄｉｎｇ）５分後（ＰＬＡが完全に溶解）、ホッパー（ｈｏｐｐｅｒ）に投入する方法を取った。運転条件は１８０℃、６０ｒｐｍで１０分間行った。得られたＰＬＡ樹脂は、後述する等温ＤＳＣ分析を行って各結晶化温度による結晶化挙動を確認した。
Examples and Comparative Examples Melt blending was performed using a Haake mixer. Specifically, 65 g of PLA pellets (NatureWorks 4032D; weight average molecular weight about 200,000) were added, and the first and second nucleating agents listed in Table 1 below were added according to their respective contents. The nucleating agent in powder form was mixed with the PLA pellets and added, and the nucleating agent having a melting point lower than the process operating temperature (180 ° C.) was added to the hopper after 5 minutes of blending (when PLA was completely dissolved). The operating conditions were 180 ° C., 60 rpm, and 10 minutes. The obtained PLA resin was subjected to isothermal DSC analysis described below to confirm the crystallization behavior at each crystallization temperature.
実験例
前記製造した第１核剤、第２核剤およびポリラクチド樹脂組成物に対して以下の方法で物性を測定した。
Experimental Examples The physical properties of the first nucleating agent, the second nucleating agent and the polylactide resin composition prepared above were measured by the following methods.
１）重量平均分子量
ＧＰＣ（Ｇｅｌ Ｐｅｒｍｅａｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ）装備を利用して数平均分子量（Ｍｎ）、重量平均分子量（Ｍｗ）を算出し、オリゴマー（ｏｌｉｇｏｍｅｒ）分子量分布（Ｍｗ／Ｍｎ）を測定し、具体的な測定条件は下記のとおりである。
－カラム：ＰＬｇｅｌ Ｍｉｘｅｄ Ｅ ｘ ２
－溶媒：ＴＨＦ
－流速：０．７ｍＬ／ｍｉｎ
－試料濃度：３．０ｍｇ／ｍＬ
－注入量：１００μｌ
－カラム温度：４０℃
－検出器（Ｄｅｔｅｃｔｏｒ）：Ｗａｔｅｒｓ ２４１４ ＲＩＤ
－スタンダード（Ｓｔａｎｄａｒｄ）：ＰＳ（ポリスチレン）
1) Weight average molecular weight Using a GPC (Gel Permeation Chromatography) device, the number average molecular weight (Mn) and weight average molecular weight (Mw) were calculated, and the oligomer molecular weight distribution (Mw/Mn) was measured. The specific measurement conditions are as follows.
- Column: PLgel Mixed Ex 2
Solvent: THF
Flow rate: 0.7 mL / min
- Sample concentration: 3.0 mg / mL
Injection volume: 100 μl
- Column temperature: 40°C
-Detector: Waters 2414 RID
-Standard: PS (polystyrene)
２）ＤＳＣ（ｄｉｆｆｅｒｅｎｔｉａｌ ｓｃａｎｎｉｎｇ ｃａｌｏｒｉｍｅｔｒｙ）
実施例と比較例で製造したＰＬＡ樹脂のそれぞれを、１次加熱（１ｓｔ ｈｅａｔｉｎｇ）を通じて２００℃で２０分間完全に溶融させて熱履歴を除去した。次に、各結晶化温度（１００～１３０℃）まで１００℃／分で最大限急速に冷却させた後、各結晶化温度で温度を維持してヒートフロー（Ｈｅａｔ Ｆｌｏｗ）を観察して、結晶化半減期を測定した。また、次の式を利用して結晶化度Ｘｃを計算した（１００％ ｃｒｙｓｔａｌｌｉｎｅ ＰＬＡ ΔＨｍ＝９３Ｊ／ｇ）。
2) DSC (differential scanning calorimetry)
Each of the PLA resins prepared in the examples and comparative examples was completely melted at 200°C for 20 minutes in the first heating to remove thermal history. Then, it was cooled as rapidly as possible to each crystallization temperature (100-130°C) at 100°C/min, and the heat flow was observed while maintaining the temperature at each crystallization temperature to measure the crystallization half-life. The degree of crystallinity Xc was calculated using the following formula (100% crystalline PLA ΔHm=93 J/g).
－結晶化度：（冷却過程での発熱ピーク（ｐｅａｋ）面積、ΔＨｃ）／（１００％ ｃｒｙｓｔａｌｌｉｎｅ ＰＬＡ ΔＨｍ）
前記結果を下記表１に示した。
The results are shown in Table 1 below.
前記表１に示されているように、本発明により第１核剤と第２核剤を同時に使用した実施例の場合、比較例に比べて結晶化度は同等または類似の水準であるが、結晶化半減期が顕著に小さいことを確認することができた。 As shown in Table 1, in the case of the examples in which the first and second nucleating agents were used simultaneously according to the present invention, the crystallinity was at the same or similar level compared to the comparative examples, but the crystallization half-life was significantly shorter.
Claims (10)
前記ポリラクチド樹脂組成物は、１００～１３０℃の結晶化温度で結晶化半減期が２分以下である、
ポリラクチド樹脂組成物。 A polylactide resin composition comprising: a polylactide resin; a first nucleating agent; and a second nucleating agent,
The polylactide resin composition has a crystallization half-life of 2 minutes or less at a crystallization temperature of 100 to 130°C.
Polylactide resin composition.
請求項１に記載のポリラクチド樹脂組成物。 The polylactide resin composition has a crystallization half-life of 1.3 minutes or less at a crystallization temperature of 100 to 130°C.
The polylactide resin composition according to claim 1.
請求項１に記載のポリラクチド樹脂組成物。 The polylactide resin composition has a crystallinity of 35% or more at a crystallization temperature of 100 to 130°C.
The polylactide resin composition according to claim 1.
請求項１に記載のポリラクチド樹脂組成物。 The first nucleating agent is uracil;
The polylactide resin composition according to claim 1.
請求項１に記載のポリラクチド樹脂組成物。 The first nucleating agent is contained in an amount of 0.1 to 5 wt % based on the total weight of the polylactide resin composition.
The polylactide resin composition according to claim 1.
請求項１に記載のポリラクチド樹脂組成物。 The second nucleating agent is a compound containing a lactide oligomer structure.
The polylactide resin composition according to claim 1.
請求項１に記載のポリラクチド樹脂組成物：
［化学式１］
Ｌは、下記であり、
ｎ１は、１～３０の整数であり、
Ｒは、下記の化学式２で表される置換基であり、
［化学式２］
Ｒ’は、水素、またはアセチルである。 The second nucleating agent is a compound represented by the following formula 1:
The polylactide resin composition of claim 1 :
[Chemical Formula 1]
L is as follows:
n1 is an integer from 1 to 30,
R is a substituent represented by the following chemical formula 2:
[Chemical Formula 2]
R' is hydrogen or acetyl.
請求項１に記載のポリラクチド樹脂組成物。 The weight average molecular weight of the second nucleating agent is 1,000 to 50,000;
The polylactide resin composition according to claim 1.
請求項１に記載のポリラクチド樹脂組成物。 The weight average molecular weight of the polylactide resin is 70,000 to 400,000.
The polylactide resin composition according to claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2022-0035553 | 2022-03-22 | ||
| KR1020220035553A KR20230137738A (en) | 2022-03-22 | 2022-03-22 | Polylactide resin composition having excellent crystallization half-time, and method for preparing thereof |
| PCT/KR2023/002704 WO2023182687A1 (en) | 2022-03-22 | 2023-02-27 | Polylactide resin composition having excellent crystallization half-time, and method for preparing same |
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| EP (1) | EP4332159A1 (en) |
| JP (1) | JP2024520576A (en) |
| KR (1) | KR20230137738A (en) |
| CN (1) | CN117500871A (en) |
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| US20030038405A1 (en) * | 2001-08-20 | 2003-02-27 | Bopp Richard C. | Method for producing semicrystalline polylactic acid articles |
| JP4130695B2 (en) * | 2006-10-11 | 2008-08-06 | 花王株式会社 | Biodegradable resin composition |
| JP5794498B2 (en) * | 2009-09-10 | 2015-10-14 | 国立研究開発法人産業技術総合研究所 | Polylactic acid resin composition |
| JP2016011388A (en) * | 2014-06-30 | 2016-01-21 | 株式会社リコー | Polylactic resin composition, and molded article |
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| KR20230137738A (en) | 2023-10-05 |
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| CN117500871A (en) | 2024-02-02 |
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| EP4332159A1 (en) | 2024-03-06 |
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